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  • C07D203/00—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom
  • C07D203/04—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings
  • C07D203/06—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
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  • C07C323/11—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
  • C07C323/12—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
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  • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
  • C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
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  • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
  • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
  • C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
  • C07D295/182—Radicals derived from carboxylic acids
  • C07D295/185—Radicals derived from carboxylic acids from aliphatic carboxylic acids
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  • C07D295/22—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with hetero atoms directly attached to ring nitrogen atoms
  • C07D295/26—Sulfur atoms
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  • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
  • C08B11/00—Preparation of cellulose ethers
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  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
  • D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
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  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
  • D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
  • D06M13/256—Sulfonated compounds esters thereof, e.g. sultones
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  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
  • D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
  • D06M13/272—Unsaturated compounds containing sulfur atoms
  • D06M13/278—Vinylsulfonium compounds; Vinylsulfone or vinylsulfoxide compounds

Definitions

• This invention relates to a method of stepwise modifying polymeric materials with a polyfunctional reactant in which the functional groups have different reactivity, and to the resulting modified materials so produced; and, more particularly, to a method of cross-linking polymeric materials with the aforementioned polyfunctional reactant wherein one functional group reacts with the polymeric material under one set of reaction conditions and a second functional group reacts subsequently with the material under a different set of reaction conditions, and to the cross-linked materials so produced.
• the invention further relates to a new and improved group of polyfunctional eactants and the method of making the same.
• polymeric materials to improve particular properties by treating the materials with a polyfunctional reactant
• a polyfunctional reactant is well known.
• One example is the crass-linking of linear polymers to form a three-dimensional network.
• cellulosic textiles have been crosslinked with polyfunctional sulfones, epoxides, N-methylol amides, and the like, in order to modify the properties of the textiles, including those of dimensional stability, resilience, flat-drying, and the like, which properties are not possessed by the textiles in the unmodified state.
• cross-linking reagents which have been used to date have similar functional groupings, and thus, while the cross-linking process does permit some control of the extent and rate of the reaction by adjusting concentrations, catalysts, temperatures, and the like, it is generally impossible to exercise sufficient control over the cross-linking reaction because the reactive groups combine with the polymer at similar rates, and a three-dimensional network is formed.
• a cellulose solution e.g., viscose
• cellulosic fibers are cross-linked by reacting with a cross-linking agent, their elongation at the breaking point is severely reduced and the resulting fibers therefore difiicult to spin into yarns.
• the crosslinking modification of the fibers is usually carried out as a final step after the end product, such as the textile fabric, has been formed, and usually after the dyeing of the fabric.
• the usefulness of the cross-linking processes is limited, their scope restricted, and the modification of the cellulosic fibers must be carried out by the fabric finishers and not by the fiber manufacturers, as would be desirable in some instances.
• active hydrogen any reactive hydrogen atom which is capable of being added to, being replaced by, or entering into reaction with the functional group of the reagent employed.
• Another object of the invention is to provide a polymer having an unsymmetrical bifunctional cross-linking agent attached thereto as the result of reaction between an active hydrogen atom of the polymer and one of the functional groups of the agent whereby the physicomechanical properties of the polymer, such as a cellulosic material, remain substantially the same as those of an untreated polymer, and the change in properties does not occur until the other functional group of the cross-linking agent is reacted with another active hydrogen atom of the polymer and the agent becomes in effect a cross-link.
• Another object of this invention is to provide processes for forming the aforesaid new and useful polyfunctional cross-linking agents.
• a further object of this invention is to provide polymeric materials having an unsymmetrical polyfunctional compound attached thereto by the reaction of one functional group with an active hydrogen of the material, which treated polymeric material is capable of further and subsequent reaction between the remaining functional groups and other hydrogen atoms of the material whereby the properties of the material may be modified by such subsequent reaction.
• one feature resides in modifying a polymeric material containing active hydrogen atoms by reacting the material with an unsymmetrical bifunctional modifying agent having one functional group reacting with the active hydrogen atoms of the polymeric material under exceedingly mild conditions and the other reactive group entering into reaction with the active hydrogen atoms when heated to a temperature of at least 100 C. in the presence of a suitable catalyst.
• one functional group of the reagent can be inert under alkaline conditions and react with the active hydrogen atoms of the polymeric material under acidic conditions, while the second functional group reacts under alkaline conditions, so that a stepwise reaction can be achieved by providing acidic and alkaline conditions of catalysis in separate steps.
• a specific feature resides in having the unsymmetrical polyfunctional cross-linking agent of the invention contain at least one reactive group which is a vinyl sulfone donor and is reactive at ambient temperatures with the active hydrogen atoms of cellulose and in having the cross-linking agent contain another reactive group which is an oxyethyl group which reacts at higher temperatures, so that substantially complete control over the modification process can be achieved.
• the polymers are reacted with an unsymmetrical polyfunctional compound of the formula wherein Q is an organic radical, X is a functional group and Y is a functional group which differs from X in structure and reactivity.
• the reaction takes place under conditions whereby only one functional group reacts with an active hydrogen of the polymer, and subsequently the treated polymer is subjected to a set of reaction conditions wherein the other functional group of the compound reacts with still another active hydrogen of the polymer.
• the compound XQY can be attached to the cellulose molecules by reaction of the functional group X with the hydrogen in a hydroxyl group of the cellulose molecule under a particular set of reaction conditions.
• the treated material is subjected to the particular reaction conditions which enable the functional group Y to react with an active hydrogen of the cellulose molecules.
• the reaction conditions may be the same but X and Y have the properties of reacting at widely different rates under such conditions.
• R is selected from the group consisting of hydrogen and lower alkyl
• A is selected from the group consisting of
• Z is a bivalent organic radical selected from the group consisting of alkylene, aralkylene, the residue of a diamine N .Y ...1TI R R in which Y is a divalent organic radical and R has the same definition as above, and the residue of a heterocyclic diamine A -N D N- V in which the two nitrogen atoms are part of the heterocyclic ring D,
• R" is a member selected from the group consisting in which A is selected from the group consisting of a polar residue derived from a reagent of weak nucleophilic character and the aziridinyl residues and (3) where R in each of the formulas has the meaning defined above, namely, a member selected from the group consisting of hydrogen and lower alkyl.
• a polymeric material having active hydrogen atoms such as a cellulosic material
• a polymeric material having active hydrogen atoms such as a cellulosic material
• the new and novel sulfone and sulfonamide compounds of the invention having the formula wherein R, R and R", Z and n have the same definitions as in Formula I.
• polar residues A which can be present in the compounds represented by the Formulas I and II as Well as IIa are groups derived from reagents of Weak nucleophiliccharacter. More specifically, the polar residues are selected from the group consisting of the anion of a strong acid (ionization constant and the cation of a weak base (ionization constant 10- Specific examples of A are the following: When A is the anion of a strong acid:
• OSO M sulfate residue where M is selected from the group consisting of alkali and ammonium --SSO M thiosulfate residue, where M has the same meaning as above -OCOCH acetate residue, and the like.
• Nucleophilic character is defined as the tendency to donate electrons or share them with a foreign atomic nucleus. (Gilman, Organic Chemistry, second edition, vol. II, p. 1859.)
• the reaction of the new unsymmetrical. compounds with cellulosic fibers is significant since processes for crosslinking the cellulose molecules impart many highly desirable properties to textile materials manufactured from cellulosic fibers.
• the present invention will be illustrated by the reaction of the unsymmetrical sulfones of the above formulas with cellulosic materials, including cotton fabrics and regenerated cellulosic fabrics, although it must be understood that the compounds of generic Formula I can be used as stepwise modifying or cross-linking agents for all polymeric materials containing a plurality of active hydrogen atoms per polymeric molecule, both cellulosic and non-cellulosic, which polymeric materials include natural fibrous polymers such as cellulose, wool, silk, and the like; synthetic fibrous polymers such as polyarnides, polyvinyl alcohol fibers, and the like; natural non-fibrous materials such as starch, gelatin, and the like; and synthetic non-fibrous polymers such as polyvinyl alcohol resin, polypeptides, and the like.
• the aforesaid polymeric materials having active hydrogen atoms may be reacted at any stage of their developmentincluding as solutions, as fibers, as yarns, as textile fabrics and the likewith one of the functional groups of the modifying agent, and, subsequently, at another stage of development, the treated polymeric material is reacted under conditions such that another different functional group of the modifying agent reacts with the polymeric material so as to etfect a cross-linking of the polymers and the formation of a three-dimensional network of polymers joined or cross-linked by the modifying agent.
• the unsymmetrical polyfunctional modifying agent can be attached by one of the functional groups to the polymeric material in fiber form and, after the fiber has been converted to yarns and subsequently to a fabric, the fabric may be subjected to the proper reaction conditions which permit the other functional group on the modifying agent to react with an active hydrogen on the fabric polymer and effect cross-linking, thus modifying the properties of the fabric.
• the material being treated include polymers having active hydrogen atoms and thus the process of the invention is also applicable to blends of polymeric materials containing the active hydrogen atoms with materials having no active hydrogens, including fabrics made from a blend of two or more fibrous polymers.
• novel compounds of Formula I are those having the formula and A is selected from the group consisting of a polar residue derived from a reagent of weak nucleophilic char- 7 8 acter, such as the cation of a weak base (e.g., NC H presence of a suitable catalyst.
• a weak base e.g., NC H presence of a suitable catalyst.
• a strong acid e.g., SSO Na, apparent, cross-linking of polymeric chains can be carried thiosulfate; -OSO Na, sulfate
• aziridinyl radicals e.g., SSO Na, apparent, cross-linking of polymeric chains.
• the compounds corresponding to Formulas III and IV The compounds shown in Formulas III and IV are charin which R and R are hydrogen can be prepared by the acterized by the presence of the beta-oxyethyl sulfone following reactions:
• MOH is preferably an alkali metal conditions and at elevated temperatures. They are further hydroxide, but any alkaline compound having a dissociacharacterized by the presence of the vinyl sulfone grouption constant greater than about 10- will be satisfactory ing (Formula III) and the corresponding saturated dein the aforesaid reaction.
• the reactions illustrated by the foregoing equations can be carried out at ambient temperature in the presence of water under conditions which do not remove or affect the (VI) HOCHZCHZSONHZOHZIFQH beta-oxyethyl sulfone grouping.
• Such polymeric reaction 01 products can be converted to end products which can be cross-linked at any desired stage of processing by effecting
• the beta-hydroxyethyl-beta chloroethyl sulreaction of the beta-oxyethyl sulfone with unreacted polyfone can be reacted with other compounds to convert it mer molecules as shown in the following equation: to other saturated derivatives of polar character.
• the group (VIII) ROCHZCHzCONEICIJZNEICOCHZCH2 2 2 which can be obtained for example simply by the addior, alematively S02CH2CH2A is reacted at ambient tion of one mole of alcohol to one mole of the symmetritemperatures in the presence of an aqueous alkali to form cal unsaturatfid compound hylene bis acrylamide, a side chain on the polymer.
• some and related Compounds P p in Similar manner from his acrylamides and bis vinyl sulfonamides of other bis secondary and his primary amines.
• ketones such as those CQHOCECHZSONIJHCHO R shown in Formulas IX and IX-a below.
• cellulose molecules are converted to a cellulose ether having the formula:
• R is selected from the group consisting of hydro- (X) gen, lower alkyl and lower acyl
• R is a member selected I from the group consisting of hydrogen and lower alkyl.
• the compounds of Formula VII can be prepared either ROCHzCH-C ON from the compounds of Formula III by addition of a threemembered heterocyclic imino compound as shown by way of example in Equation 7, H
• the two steps of the cross-linking process are both carried out under essentially anhydrous conditions at elevated temperature, but one functional group is reacted under alkaline conditions, while the second is reacted under acidic conditions.
• processing conditions required to carry out the stepwise cross-linking employing the unsymmetrical reagents of the present invention depend on the chemical structure of the reagent selected.
• Example 1 Preparation of 2 chloroethyl 2' hydroxyethyl sulfone 154 grams (1 mol) of anyhydrous bis-( 2 hydroxyethyl) sulfone were dissolved in 500 g. of dimethyl ether of ethylene glycol and 79 g. (1 mol) of pyridine were added thereto. 95 g. (0.8 mol) of thionyl chloride were then added with stirring and cooling. The temperature was maintained at -45 C. and the addition took minutes. The mixture was then refluxed for 30 minutes at 8285 C.
• reaction mixture was poured into water, and the organic phase was separated. The organic phase was then dried over Na SO and the solvent was removed by distillation, leaving 66 grams of crude product in the form of a brown liquid.
• Example 2 Preparation of 2 hydroxyethyl sulfonyl ethyl pyridinium chloride HO CHlCHiSOjCHiCHglTICiHA 69 grams (0.4 mol) of 2 chloroethyl 2hyroxyethyl sulfone, 28 grams (0.4 mol) of pyridine, and 150 grams of isopropanol were refluxed with stirring at 8892 C. for 12 hours. A tan solid precipitated in the course of reaction, indicating that essentially all of the organic chloride which was present was converted to ionic chloride. The solvent layer was decanted, and the precipitate was washed with acetone and ether on a filter. 61 grams of light tan crystalline product were obtained.
• the equivalent weight was determined by electrometric titration with standard NaOH solution (end pt: pH 10.5).
• the distillate weighed 214 grams, corresponding to a yield of 89.5% of the theoretical.
• Example 4 Preparation of 2 methoxyethyl 2' hydroxyethyl sulfide 273 grams (3.5 mols) of 2-mercaptoethanol were added to grams (3.5 mols) of sodium hydroxide dissolved in 300 grams of ethanol. 331 grams (3.5 mols) of 2 methoxyethyl chloride were added dropwise with stirring under a blanket of nitrogen over a period of 5 hours. The temperature was kept below 40 C. After the addition was completed, the mixture was stirred an additional 3 hours. The precipitated sodium chloride was filtered off, and ethanol and water were removed by stripping under reduced pressure. The product was then distilled. B.P.: 104l07 C. at 6 mm. The distillate was a colorless liquid.
• the product was obtained as a light yellow liquid which weighed 200 grams and contained only a very small amount of oxidizable sulfur (0.25%). The yield was 89.5% of the theoretical.
• Example 7 Preparation of 2 rnethoxyethyl sulfonyl ethyl pyridinium chloride CHaO CHzCHnSOgCHgCHgIIICsHa 200 grams (1.07 mols) of 2 metl1oxyethyl-2-chloroethyl sulfone (product of Example 6) were mixed with 250 grams of isopropanol and 85 grams (1.07 mols) of pyridine, and refluxed for 6 hours at 80-90 C., at which time essentially all of the organic chloride present was converted to ionic chloride. This isopropanol was removed under reduced pressure, and the crystalline residue was washed with acetone and ether on a filter.
• the weight of the white crystalline product so obtained was 262.8 grams, corresponding to a yield of 91% of the theoretical.
• the equivalent weight was determined by electrometric titration with a standard NaOH solution.
• Example Sr-Preparation of 2 methoxyethyl, 2-thiosulfatoethyl sulfone 93.2 grams (0.5 mol) of 2 methoxyethy-l 2'-chloroethyl sulfone (product of Example 6) were mixed with 93 grams of ethanol, and a solution of 124 grams (0.5 mol) of sodium thiosulfate pent-ahydrate in 124 grams of water was added. The mixture so obtained was refluxed with stirring for 4 hours, until essentially all of the organic chloride was converted to ionic chloride. The reflux temperature of the mixture was -90 C. After the refluxing, conversion was achieved, as indicated by titration for free thiosulfate ion. The reaction product was not isolated in crystalline form, but the ethanol was distilled ofl and the residual aqueous solution was analyzed as follows:
• Example 10 Preparation of 2 methoxyethyl 2' aziridino ethyl sulfone 29.0 g. (0.19 mol) of 2 methoxyethyl vinyl sulfone (product of Example 9) were added to 13.2 g. (0.3 mol) of ethylene imine keeping the temperature at 2930 C. by cooling with an ice bath. The time of the addition was 25 minutes, and stirring for 60 minutes at room temperature after completing the addition was sufficient to achieve complete reaction. The excess ethylene imine was distilled otf and the residual yellow liquid weighed 35.1 g. The equivalent weight determined by titration with standard acid was 208 (calcd.: 193). The equivalent weight determined by thiosulfate titration (described in JACS 77, 5918-22 (1955)) was 211. The yield of product was 88.6% of the theoretical.
• Example l0-A.-Preparation of 2-methoxypropionamidomethyl acrylamide 42.1 g. of 60% aqueous N-methylolacrylamide (0.25 mol) and 14.0 g. of 37% aqueous HCl were added dropwise at room temperature to a solution of 51.5 g. of 2- methoxypropionamide (0.5 mol) in 50 g. of water. The mixture was then stirred for 1 hour, and allowed to stand at room temperature overnight. The reaction mixture was then cooled to 5 C. and neutralized to pH 6.0 by the gradual addition of Na CO The white crystalline pre cipitate formed was filtered, and twice recrystallized from isopropanol. M.P. 155 157 C.
• Example 2 the reaction occurs at a temperature of from 80 to 90 C. in a period of from 412 hours and the reactants are present in equimolar proportions.
• Example 10 the imine is present in excess and the reaction is conducted at low temperatures of 2930 C. and then completed at room temperature. Variations in temperatures and times will be readily apparent.
• Example 11 Reactions of Z-hydroxyethyl sulfonyl ethyl pyridinium chloride (product of Example 2) with cotton fabric
• a sample of cotton fabric (known as 80 x 80 print cloth) was impregnated with a aqueous solution of the product of Example 2 on a laboratory padder, setting the rolls at such a pressure as to give a 100% wet pickup. 0.25 gram of reagent was thus deposited on each gram of cotton fabric. The impregnated fabric was framed to the original dimensions and dried in a forced draft oven at 8090 C., then treated by padding with a 5.5% sodium hydroxide solution.
• the amount of NaOH solution picked up by the fabric was such (76%) as to yield a 1.04 mols ratio of NaOH to reagent on the fabric.
• the fabric was rolled and allowed to stand wet at room temperature for 60 minutes, care being taken to prevent evaporation of water by covering the roll with poly-ethylene or other non-porous material.
• the fabric was rinsed with 1% acetic acid to neutralize residual NaOH, and washed at 6070 C.
• the reaction described yielded a 3.6% increase in fabric weight, forming the product CH OH 1% od described in the Technical Manual of the American Association of Textile Chemists and Colorists, 1960' edition, pp. 165l67, Tentative Test Method 664959, ASTM designation D 129553T.
• Example 12 Reactions of 2 methoxyethyl sulfonyl ethyl pyridiniurn chloride (product of Example 7) with cotton fabric (A) Samples of 80 x 80 print cloth were padded with to 20% solutions of the reagent to give 36.6 and 18.4% reagent, based on the weight of the dry fabric, respectively. The mol ratio of NaOH to reagent was thus 1.19 and 1.18 respectively. The samples were rolled, wrapped in polyethylene sheeting and allowed to stand at room temperature for 30 minutes. After the reaction was completed, the fabrics were rinsed in a 1% acetic acid solution then washed in a detergent solution at -70 C., rinsed in cold water, dried, conditioned and weighed analytically to determine the weight increase due to treatment.
• Example 12(A) Example 12(B) Reagent concentration, percent based on weight of fabric 36. 6 18. 4 36. 6 18. 4
• the sulfur content of the fabric so treated was equivalent to the observed weight increase.
• the physical properties of the treated cotton fabric were essentially identical with those of the untreated fabric, since in the modification of the fiber only one reactive grouping of the reagent was involved and side chains were introduced without incipient cross-linking or formation of a three-dimensional network.
• Example 13 Reactions of 2 methoxyethyl thiosulfatoethyl sulfone (product of Example 8) with cotton fabric
• a sample of x 80 cotton print cloth was padded with an aqueous solution of the reagent to give 0.2 gram of reagent per gram of fabric, and dried at 80-90" C.
• the fabric was'then padded with a 4% NaOH solution at 75.5% wet pickup, giving 0.03 gram of NaOH per gram of fabric. This was equivalent to 1.08 -mols of NaOH per mol of reagent.
• the wet fabric was rolled, wrapped in polyethylene sheeting and allowed to stand for 30 minutes at room temperature. After this reaction period, the fabric was rinsed in a 1% solution of acetic acid, then washed in detergent solution at 6070 C., rinsed in water, dried, conditioned and weighed to determine the weight increase.
• Example l4.-Reactions of 2 methoxyethyl 2' thiosulfatoethyl sulfone (product of Example 8) with regenerated cellulose (rayon) fabric A sample of viscose rayon fabric was padded with an aqueous solution of the reagent to give 0.2 gram of reagent per gram of fabric, and dried at 80-90" C. The fabric was then treated with a 4.7% solution of poassium hydroxide at 95% wet pickup, giving a 1.15 mol ratio of KOH to reagent on the fabric. The fabric was rolled, wrapped in polyethylene sheeting and allowed to stand wet at room temperature for 30 minutes. It was then neutralized in 1% acetic acid, washed, dried, conditioned and weighed.
• Example 14 employing the product of Example 7 instead of the prodnot of Example 8, the following results were obtained:
• Example 16 Reactions of 2-methoxyethy1 2aziridinoethyl sulfone (product of Example 10) with cotton fabric Samples of 80 x 80 cotton print cloth were padded with the following aqueous solutions on a laboratory padder:
• the acid catalyzed step induced opening of the aziridine ring, and formation of a cross-linked product Cell-OCH CH SO CH CH NHCH CH OCcll which exhibited greatly enhanced crease recovery over the side chain reaction product formed in the alkali catalyzed first step.
• Example 17 Reactions of Z-methoxyethyl sulfonyl ethyl pyridinium chloride (product of Example 7) with cotton and rayon (A)
• Cotton yarn skeins were padded with a 25% aqueous solution of a methoxyethyl sulfonyl ethyl pyridinium chloride (the product of Example 7) to give l9.95% reagent based on the weight of yarn. After drying at 80- C., the skeins were padded with a 5% solution of NaOH to give 5.25% NaOH based on the weight of the yarn. The mol ratio of NaOH to reagent was thus 1.75.
• the skeins were wrapped in polyethylene sheeting and allowed to stand at room temperature for 30 minutes. They were then rinsed in 1% acetic acid and washed in a non-ionic detergent solution at 6070 C., rinsed in cold water, conditioned and weighed analytically to determine the weight increase due to the treatment.
• the yarn skeins were knitted into tubing which was then padded with a 3% KHCO solution, dried at 80 C. and cured for 3 minutes at C. Routine rinse and wash followed the curing step and the changes in physical properties were determined.
• the treated skeins were knitted into tubing, padded with a 3% solution of KHCO dried at :80" C., and cured for 3 minutes at 150 C. Routine rinse and wash followed the curing step and the changes in the physical properties of the yarn were determined.
• a sample of 1.5" Pima cotton fiber was carded to give a web suitable for padding treatment. The web was encased in Dacron polyester sheeting and padded with a 25% solution of 2-methoxyethyl sulfonyl ethyl pyridinium chloride (product of Example 7) to give 45% reagent on the weight of fiber. After drying at 80-90' C.
• the web was padded with a 5% solution of NaOH to give 19 7.5 NaOH on the weight of the fiber.
• the mol ratio of NaOH to reagent present on the fiber was 1.1.
• the fiber sample was wrapped in polyethylene sheeting and allowed to stand at room temperature for 30 minutes. After this reaction period, the fiber web was rinsed in 1% acetic acid, then washed in warm water, rinsed and dried.
• the cotton fiber was processed without difiiculty by carding again, drawing, spinning at 7500 rpm. and knitting.
• the knitted fabric so obtained was padded with a 3% solution of KHOO dried at 80 C. and cured for 3 minutes at 150 C. Routine rinsing and washing followed the cur ing step, and the physical properties of the yarn manufactured from the treated fiber were determined before and after the cross-linking step which was carried out after knitting.
• Example 18(B) An attempt was made to obtain results comparable to those outlined in Example 18(A) by cross-linking cotton fiber in a single step, and subsequently converting the treated fiber into yarn and knitted fabric.
• a sample of the same 1.5 Pima cotton fiber used in Example 18(A) was carded to give a web suitable for padding treatment.
• the web was encased in Dacron polyester sheeting and padded with an aqueous solution containing 6% bis(beta hydroxyethyl) sulfone and 3.9% KHCO as catalyst. 10% cross-linking agent was deposited based on the weight of the cotton fiber.
• Example 18(A) After drying at 80-90 C., the web was cured at 150 C. for 3 minutes. Routine rinse and wash followed the curing. An attempt was made to process the treated fiber sample into yarn and knitted fabric by the procedure described in Example 18(A). The carding did not present unusual difiiculties, but the drawing resulted in an unsatisfactory web which had a flaky appearance from fibers dispersed throughout. Spinning of this web into yarn was extremely difficult. Even when the spindle speed was dropped from 7500 r.p.m. (which was the speed used in Example 18(A)) to 5500 r.p.m., the end would not stay up for any length of time. Some yarn was spun with great difiiculty, but it was so weak that it could not be knitted.
• Example 18 The experiments described in Example 18 illustrated the great advantage of the invention, namely the possibility of introducing a cross-linking reagent into fiber, prior to processing, by reacting one functional group only, and without altering the behavior of the fiber in processing, and completing the cross-linking reaction at any desired stage in the manufacturing process.
• Example 19 20.0 grams of corn starch (Corn Product Co., NY.) were added to a mixture of 180 grams of dioxane and 10 mls. of N aqueous NaOH, and stirred at room temperature for minutes. 2 grams of Z-methoxyethyl vinyl sulfone were added to the slurry and the mixture was stirred for 1 hour then allowed to stand overnight at room temperature. The slurry was filtered and the solid was dispersed in a mixture of 60 grams of dioxane, 30 grams of water and 10 grams of glacial acetic acid in order to neutralize the residual NaOH. After filtering, the solid was washed repeatedly with a dioxane-water mixture and dried.
• Example 20 20 grams of polyvinyl alcohol resin (marketed under the trade name of Elvanol 72-60 by E. I. du Pont de Nemours & Co.) were added to a mixture of grams of dioxane and 10 mls. of 5 N aqueous NaOH, and stirred at room temperature for 10 minutes. 2 grams of 2- methoxyethyl vinyl sulfone were added to the resulting slurry, and the reaction mixture was stirred for 1 hour then allowed to stand overnight at room temperature. The slurry was filtered, and the solid was dispersed in a mixture of 60 grams of dioxane, 30 grams of water and 10 grams of glacial acetic acid in order to neutralize the residual NaOH. After filtering, the solid was washed repeatedly with a dioxane-water mixture and dried.
• polyvinyl alcohol resin marketed under the trade name of Elvanol 72-60 by E. I. du Pont de Nemours & Co.
• the functional group RO of the modifying or cross-linking agent of Formula I reacts with an active hydrogen of the polymers of polymeric material being treated, such as cellulose, at temperatures of about 100 C. or higher, while the R radicals R R R R R where A is a polar residue derived from a reagent of weak nucleophilic character, will react with an active hydrogen atom of the polymers at ambient temperatures usually under alkaline conditions.
• the R radical of Formula I is either the aziridinyl group or the group CHCH'A wherein A is an aziridinyl radical
• the R" radical will react with an active hydrogen of the polymers under acidic conditions.
• stepwise modification or crosslinking of the polymers is accomplished in any desired manner or sequence.
• alkylene group includes methylene, ethylene, butylene, octylene, decamethylene, etc.
• aralkylene group includes CH C H CH
• R is a member selected from the group consisting of hydrogen, lower alkyl and lower alkanoyl
• R is a member selected from the group consisting of hydrogen and lower alkyl
• Z is a bivalent organic radical selected from the group consisting of alkylene and phenalkylene,
• n 0 or 1
• A is a quaternar ammonium group.

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• 0
  • BE BE626797D patent/BE626797A/xx unknown
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• 1962
  • 1962-01-08 US US165017A patent/US3419566A/en not_active Expired - Lifetime
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  • 1963-01-02 DE DE19631444126 patent/DE1444126A1/de active Pending
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